CN104583145A - 具无色二氧化钒涂层的热变色玻璃 - Google Patents
具无色二氧化钒涂层的热变色玻璃 Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 81
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 title claims abstract description 58
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000011521 glass Substances 0.000 title claims abstract description 21
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 31
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 16
- 229910052788 barium Inorganic materials 0.000 claims abstract description 10
- 239000011575 calcium Substances 0.000 claims description 31
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 30
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 25
- 229910052721 tungsten Inorganic materials 0.000 claims description 25
- 239000010937 tungsten Substances 0.000 claims description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000009500 colour coating Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- 239000011737 fluorine Substances 0.000 claims description 17
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 14
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
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- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 239000005357 flat glass Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
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- 239000004411 aluminium Substances 0.000 claims description 3
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- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
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- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims 1
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- 230000000694 effects Effects 0.000 abstract description 5
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- 238000001228 spectrum Methods 0.000 description 4
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- 150000001485 argon Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 238000007747 plating Methods 0.000 description 2
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- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 238000001429 visible spectrum Methods 0.000 description 2
- 229910017083 AlN Inorganic materials 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- ASRYXPOBJNMFNB-UHFFFAOYSA-N [O-2].[O-2].[V+5].[W+4] Chemical compound [O-2].[O-2].[V+5].[W+4] ASRYXPOBJNMFNB-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
本发明公开一种具热变色二氧化钒的玻璃涂层。二氧化钒的着色通过添加碱土元素，例如钙、锶、钡，而由青铜色转变为中性色(无色)。同时热变色效果保持不变。
Description
技术领域
本发明是涉及一种热变色玻璃涂层以及生产所述涂层的方法。这一类的热变色涂层具有对于电磁辐射(例如IR，VIS，UV)随温度变化的透明度，在建筑物建造过程中为作玻璃窗涂层，或者玻璃立面涂层，用以影响建筑物内部的室内气候并节省能源。
背景技术
在德国专利第DE 69910322T2号中说明了一种具有碱金属添加剂的二氧化钒玻璃涂层。二氧化钒在大约68摄氏度下产生状态改变。高于所述温度时为金属状态，主要反射红外光谱范围(500至2000纳米)的电磁辐射。低于所述温度时为半导体状态，可以让红外线射入。所述效果为热变色效果。
所述状态变化温度可以通过添加钨进行降低。当然，对可见光的透射度也会降低，所述透射度可以利用添加氟得以提高。在添加氟时其转换性能会变差。
二氧化钒具有青铜着色。这使其具有显着缺点，因为所述着色会对可见光进行过滤。因此会明显限制可见光范围的电磁辐射的透射。上述专利说明未对此给出解决方案，因为所述着色既无法通过涂层厚度，也无法通过其他涂层加以避免。
在德国专利第DE 3347918C2号中建议将二氧化钒还原为灰色的三氧化二钒。三氧化二钒在168K时具有状态变化，因此不适合用作热变色窗户玻璃涂层。适合的状态变化发生在300K至373K的范围内。
在上述两份专利说明书中，二氧化钒通过化学气相沉积法(CVD)进行涂覆。但在添加气态氟时存在缺点，因为在超过600摄氏度的离析温度下，无法有效地将氟渗入二氧化钒晶体格栅中。另一方面，在温度过低(小于400摄氏度)时，仅二氧化钒非晶型层被离析，其具有较差的转换性能。因此重要的是形成一种二氧化钒晶体层。
发明内容
上述发明的任务在于克服或者回避当前技术水平的缺点。
根据本发明，所述任务通过一种包含二氧化钒涂层的玻璃涂层加以解决。二氧化钒涂层优先添加钨及/或氟。通过单独或组合添加碱土元素，例如钙(Ca)、锶(Sr)、钡(Ba)对二氧化钒进行褪色。可以直接在二氧化钒或者在添加钨、氟或其他元素(例如碱土金属-1.HG：Li,Na,K,Rb,Cs,3.,4.,5.HG元素-例如B,Al,Ga,In,Si,Ge,Sn,Pb,P,As,Sb,Bi，以及除了Mg,Ca,Sr,Ba外的过渡金属)时在二氧化钒涂层中添加碱土元素。
在同时添加钨和氟时可以同时实现上述两种效果。这使得，一方面由于添加钨，转换温度Tc下降至室温范围。另一方面，在生产出的涂层中添加钙可以提高光线的透射度，尤其是可见光谱范围的光线透射度，光吸收边缘呈蓝色偏移。这一类涂层的光学外观随着钙含量的增加从青铜色向无色变化。
对于根据上述发明的热变色涂层而言，钨含量介于0.01至3.0原子百分比之间，优先为0.4至2.6原子百分比之间。
含钡、锶和钙(主要为钙)的碱土金属组含量介于0.01至15原子百分比之间，优先为1.0至10.0原子百分比之间。
氟含量介于0.01至2.0原子百分比之间，优先为0.5至1.5原子百分比之间。
二氧化钒涂层厚度为10至300纳米，优先为40至100纳米。
在玻璃和二氧化钒涂层之间优先嵌入一晶核层，所述晶核层即使在较低的温度(小于400摄氏度)下也可以促进二氧化钒涂层的结晶。对此可使用二氧化钛或者二氧化硅，优先为二氧化钛。
晶核层(也被称作中间层)厚度为5至200纳米，优先为10至70纳米。
添加钨或者氟或者碱土金属组(含钡、锶和钙)的二氧化钒涂层或者组合添加钨或者氟或者碱土金属组(含钡、锶和钙)的二氧化钒涂层可以通过覆盖层避免其二次氧化。由此涂覆由氧氮化铝、氧硫化锌、氧化锌和硫化锌单独或者组合形成的化合物覆盖层。此外，所述覆盖层也用作抗反射涂层，由此可以进一步改善光线透射度。
比较有利的方法是覆盖层厚度为10至300纳米，优先为40至100纳米。
生产所述涂层的方法
二氧化钒涂层使用喷雾法(喷镀)进行离析，优先使用高频或者射频阴极喷雾法或者DC-阴极喷雾法。也可以选择通过CVD，其他物理气相沉积法(PVD)、溶胶-凝胶法，以及等离子支持法进行涂覆。单独或者组合使用钒、钨、钙、锶、钡氧化元素或者氟化元素作为元素对阴极的来源。由此通过在氩气-氧气-环境下喷镀将元素转移到玻璃载体上。对此氩气和氧气的气体质量流量比优先为5.7：1.4。
在附加添加气体氟时，在氩气中添加四氟化碳(CF4)或者三氟甲烷(CHF3)。对此氩气、氧气和四氟化碳的气体质量流量比优先为5.7：1.4：0.3。类似比例在添加其他氟化剂，如CHF3时也适用。
也可以使用其他的氟化元素，例如氟化钙、氟化锶和/或氟化钡作为基质。使用氟化元素和含氟气体也是一种实施形式。
在室温至400摄氏度的离析温度下，气体首先以二氧化钛涂层作为晶核层进行附着，接着通过添加过程涂覆二氧化钒涂层。
添加添加剂后的二氧化钒涂层优先通过一覆盖层，尤其是抗反射涂层进行覆盖。
热变色涂层可用于玻璃(例如窗玻璃、玻璃管、玻璃杯)、塑料、纺织物、太阳能电池(光伏电池)、太阳能收集器(热水器)。
附图说明
图1是根据上述发明的窗玻璃热变色涂层的原理结构图。
图2是添加a)钙、b)钨和c)同时添加钨和钙的热变色二氧化钒涂层与波长相关的透射光谱。
图3是添加不同含量钙的变色二氧化钒涂层与波长相关的透射光谱。
图4是以二氧化钒为基础的不同热变色涂层的转换温度表和吸收边缘(波段间隙)表。
图5是添加钡和锶以及未添加添加剂的热变色二氧化钒涂层与波长相关的透射光谱。
具体实施方式
本发明的实施形式在下文中进行说明，其中，本发明包含所有下述单独和组合的优先使用的实施形式。
图1显示根据本发明的热变色涂层(10)如何涂覆到窗玻璃(12)上的原理结构图。对此，在所述玻璃基材(12)上通过反应高频或者射频阴极喷雾法离析出一个二氧化钛涂层(14)。由此形成的二氧化钛涂层在所述玻璃基材(12)上构成一晶核层。
高频发生器在喷雾时的功率在离析二氧化钛涂层时优先介于100至600W之间(等于1.2至7.4W/cm2)，优选为300W(等于3.7W/cm2)。离析温度优先为室温至600摄氏度，优选为大约300摄氏度。
接着将包含钨或者钙的钒-对阴极或者二氧化钒-对阴极通过反应高频或者射频阴极喷雾法在二氧化钛涂层上涂覆二氧化钒涂层。二氧化钒涂层(16)为热变色层。所述涂层包含大约3.3％的钙和0.2％的钨以及0.3％的氟，其他为二氧化钒。所述涂层也可以包含8.9％的钙和0.4％的钨，其他为二氧化钒。此外，所述涂层也可以包含8.9％的钙，其他为二氧化钒。同时涂层也可以包含约9％的锶，其他为二氧化钒。或者涂层包含9％的钡，其他为二氧化钒。
在离析已添加添加剂的二氧化钒涂层时，高频发生器的喷雾功率介于100至600W之间(等于1.2至7.4W/cm2)，优选为300W(等于3.7W/cm2)，离析温度优先介于100至600摄氏度之间，优选为大约400摄氏度。
同时添加氟和含钡、锶以及钙的碱土金属组的二氧化钒涂层或者同时添加钨和含钡、锶以及钙的碱土金属组的二氧化钒涂层包含系列优先使用的热变色涂层公式，其中M表示相应的碱土金属：
a)V1-X-YWXMYO2
b)V1-YMYO2-ZFZ
也可以选择通过添加氟、钨和含钡、锶以及钙的碱土金属组构成三组份添加的二氧化钒涂层。其组成通过以下公式进行说明，其中M表示相应的碱土金属：
c)V1-X-YWXMYO2-ZFZ
添加其他的元素会形成其他的公式和重量比。
接着在已热变色添加过程的所述二氧化钒涂层(16)上涂覆同样适用高频-阴极喷雾法离析的覆盖层或者覆盖涂层(18)，所述涂层优先由硫化锌组成。此外，也可以使用氧氮化铝、氮化铝、氧化铝、氧硫化锌或者氧化锌以及上述化合物的混合物(含硫化锌)代替硫化锌。所述覆盖涂层(18)用于防止所述热变色涂层(16)出现二次氧化，并用作抗反射涂层，对此主要提高可见光谱范围的光线透射度。
在离析硫化锌覆盖涂层时，高频发生器的喷雾功率介于100至600W之间(等于1.2至7.4W/cm2)，优选为200W(等于2.5W/cm2)，离析温度优先介于室温至400摄氏度之间，优选为室温。
图2显示的是添加钙或者同时添加钨和钙的、利用高频阴极喷雾设备在玻璃上离析的所述二氧化钒涂层(16)与波长相关的透射度，无二氧化钛涂层(14)和抗反射覆盖层。此外，为进行比较，还说明了一种仅添加钨的二氧化钒涂层。所述涂层在大约600摄氏度的离析温度(未添加气态氟)进行生产。可以看出，在20摄氏度的低温状态下对三个涂层进行测量，在100摄氏度的高温状态下对三个涂层进行测量。仅添加钙的涂层与仅添加钨的涂层相比在300至2500nm的范围内具有明显更高的透射度。因此，同时添加钙和钨的涂层在300至2500nm的范围内与仅添加钙的涂层具有更低的透射度，但与仅添加钨的涂层具有更高的透射度。尤其是低温和高温状态之间的透射度差异与其他涂层相比明显更大。
图3显示在高频阴极喷雾设备上添加不同含量钙的、具有20nm厚度的二氧化钛中间层(14)，但无抗反射覆盖层的离析二氧化钒涂层(16)与波长相关的透射性能。所述涂层在大约400摄氏度的离析温度下进行生产。通过曲线比较可以看出，两种状态下的透射度主要在1000至2500nm的范围内随着钙含量的升高而增大。因此，随着钙含量的升高可以看到吸收边缘的蓝色偏移，由此涂层颜色由青铜色变为无色。
图4的表格包含转换温度、吸收边缘(波段间隙)和确定的元素含量以及不同热变色涂层高频(在100摄氏度下测量)和低温状态(在20摄氏度下测量)的光谱透射度，对此涂层生产使用和测量图2所示涂层相同的条件。
如表格所示，在同时添加钨和钙时出现协同效应，也就是说同时添加的涂层具有因添加钨导致的转换温度向更低温度偏移以及因添加钙而出现的吸收边缘向更高能量或者更低波长偏移的性能。
图5说明的是添加锶和钡以及未添加添加剂的、通过高频阴极喷雾设备在玻璃上离析出的无二氧化钛中间层(14)和无抗反射涂层的二氧化钒涂层(16)与波长相关的透射性能。所述涂层在大约650摄氏度的离析温度下进行生产。确定的钡或者锶含量约为9％原子百分比。
与图2中添加钙的涂层相比，图5中添加锶和钡的涂层具有类似的转换性能。与图5中无添加剂的二氧化钒涂层相比，300至2500nm的透射度明显更高，吸收边缘在更高能量或者更低波长时才出现。
透射度，尤其是蓝色光谱范围的透射度的提高使得，热变色涂层的光学外观相对于当前技术水平下已经公开的仅添加氟或者钨的二氧化钒涂层存在本质上的改善，同时添加钨或者氟可以讲转换温度偏移至室温范围。如图3所示，相比仅添加钨的二氧化钒涂层，即使在高温状态下，根据本发明的热变色涂层的透射度也有所提高，但高温和低温状态下的透射度差异大致相同，对于试样Ca48(见图4)甚至有所升高。
纺织物或者塑料在大约100摄氏度至200摄氏度的温度下使用已经添加添加剂的二氧化钒进行涂覆。为了获得足够优良的二氧化钒结晶度以及足够良好的热变色效果，将已经添加添加剂的二氧化钒涂层涂覆在晶核层上，除了喷雾法，也可以使用PVD或者溶胶-凝胶法。在使用溶胶-凝胶法时应注意涂层厚度应尽可能均匀。
Claims (10)
1.一种热变色涂层，特别是用于玻璃(12)的热变色涂层，且包含二氧化钒(16)，其特征在于：所述二氧化钒包含：添加碱土金属。
2.根据权利要求1的热变色涂层，其特征在于，所述碱土金属包含钙、钡及锶。
3.根据权利要求1至2任一项所述的热变色涂层，其特征在于：所述二氧化钒涂层(16)另外添加钨及/或氟。
4.根据权利要求1至3任一项所述的热变色涂层，其特征在于，所述二氧化钒涂层(16)另外包含一晶核层(14)及/或一覆盖层(18)。
5.根据权利要求1至4任一项所述的热变色涂层，其特征在于，所述晶核层(14)包含如二氧化钛、二氧化硅等化合物。
6.根据权利要求1至5任一项所述的热变色涂层，其特征在于，所述覆盖层(18)包含如氧氮化铝、氧硫化锌、氧化锌和氧化硫等化合物。
7.一种由根据权利要求1所述的热变色涂层制成的热变色玻璃涂层(10)，其特征在于：所述二氧化钒涂层(16)添加碱土金属。
8.一种将根据权利要求1所述的热变色涂层用于生产含二氧化钒涂层(16)的热变色涂层的方法，其特征在于：所述二氧化钒涂层(16)添加碱土金属。
9.根据权利要求8所述的用于生产热变色涂层的方法，其特征在于：载体通过单独的涂层，优选为已添加二氧化钒涂层(16)的晶核层(14)、覆盖层(18)，利用高频或射频阴极喷雾法或DC-阴极喷雾法进行涂覆。
10.一种将根据权利要求1所述的热变色涂层用于玻璃(例如窗玻璃、玻璃管、玻璃杯)、塑料、纺织物、太阳能电池(光伏电池)、太阳能收集器(热水器)的用途。
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| CN108351445A (zh) * | 2015-11-06 | 2018-07-31 | 柯尼卡美能达株式会社 | 热变色膜及热变色复合体 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20150036136A (ko) | 2015-04-07 |
| US9309147B2 (en) | 2016-04-12 |
| EP2864267B1 (de) | 2017-12-27 |
| KR102079411B1 (ko) | 2020-02-19 |
| DE102012012219B4 (de) | 2014-12-24 |
| EP2864267A1 (de) | 2015-04-29 |
| US20150203398A1 (en) | 2015-07-23 |
| CN104583145B (zh) | 2018-10-19 |
| WO2013189996A1 (de) | 2013-12-27 |
| DE102012012219A1 (de) | 2013-12-24 |
| JP6385923B2 (ja) | 2018-09-05 |
| JP2015527958A (ja) | 2015-09-24 |
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